Atomic-layer-chemical-vapor-deposition of films that contain silicon dioxide

ABSTRACT

Process for producing silicon oxide containing thin films on a growth substrate by the ALCVD method. In the process, a vaporisable silicon compound is bonded to the growth substrate, and the bonded silicon compound is converted to silicon dioxide. The invention comprises using a silicon compound which contains at least one organic ligand and the bonded silicon compound is converted to silicon dioxide by contacting it with a vaporised, reactive oxygen source, in particular with ozone. The present invention provides a controlled process for growing controlling thin films containing SiO 2  with sufficiently short reaction times.

REFERENCE TO RELATED APPLICATIONS

The present application is a U.S. national phase application under 35U.S.C. §371, based on PCT/FI00/01072, filed Dec. 4, 2000, and claimspriority under 35 U.S.C. §119 to Finnish Patent Application NumberFI19992616, filed Dec. 3, 1999.

The present invention relates to a method according to the preamble ofclaim 1 of producing oxide films.

According to such a method a thin film containing silicon dioxide isproduced on a growth substrate by an ALD method by bonding a vaporisablesilicon compound onto the growth substrate and converting the bondedsilicon compound to silicon dioxide.

The invention also relates to a method according to the preamble ofclaim 20 of producing multicomponent oxides (i.e. mixed oxides ortertiary oxides).

The continual decrease in the size of microelectronics components isleading into a situation in which SiO₂ can no longer be used as the gatedielectric (gate oxide) of MOSFET (metal-oxide-semiconductorfield-effect transistor) since for achieving required capacitances theSiO₂ layer should be made so thin that the tunneling current increasesdisadvantageously high from the functional point of view of thecomponent. To avoid the problem SiO₂ has to be replaced by a dielectricmaterial with higher dielectric constant. In that case a thicker layerof the dielectric material than SiO₂ can exist. Similarly thecapacitance of DRAM (Dynamic Random Access Memory) capacitors mustremain nearly constant meanwhile their decrease expeditiously in size,thus the previously used SiO₂ and Si₃N₄ have to be replaced withmaterials having higher dielectric constants than these.

Materials having sufficiently high dielectric constants are abundant,but the problem is that the considered dielectric should be stable onthe silicon surface, should most preferably be amorphous and shouldendure nearly unchanged under high post-treatment temperatures.Especially in the gate dielectric application a state where electricallyactive defects are rare should be provided at the interface of siliconand the high permittivity metal oxide. In the memory application thestructure of the capacitor dielectric must be very stable due to theapplied high activation temperatures. Due to the above mentioned factsit is preferable to admix SiO₂ to the metal oxide with a higherdielectric constant.

In its various forms Chemical Vapor Deposition (CVD) is the mostfrequently used method of producing silicon dioxide (see patentpublications JP 9306906, U.S. Pat. No. 4,845,054, U.S. Pat. No.4,981,724, U.S. Pat. No. 5,462,899, JP 20868486, JP 6158329, JP80061810, U.S. Pat. No. 4,872,947, JP 7026383, U.S. Pat. No. 5,855,957and U.S. Pat. No. 5,849,644). Mainly tetraethoxy silane (TEOS) has beenused as the silicon source material, and oxygen, water, hydrogenperoxide or ozone have been used as the oxygen source material in thepatent publications. In the conventional CVD the oxygen source materialis always brought simultaneously with the silicon source material to thegrowth substrate.

The conventional CVD method is related to the difficulty of controllingthe process, and neither a sufficiently good coverage with the thinlayers nor a good conformality is always achieved by CVD.

The invention is based to the idea that thin films containing silicondioxide are produced by the Atomic Layer Chemical Vapor Deposition(ALCVD) process, which is generally known also as Atomic Layer Epitaxy(ALE) or Atomic Layer Deposition (ALD).

ALD is a current method of growing thin films (U.S. Pat. No. 4,058,430).According to the method a thin film is grown by means of saturablesurface reactions, which are well separated from each other. Thesaturation is provided by means of chemisorption. In other words, thereaction temperature is selected as that the gaseous source material isstable at the growth temperature and additionally, it does not condenseor decompose on the surface but is capable to react selectively with thereactive sites of the surface, e.g., with the OH groups or oxygenbridges (M—O—M) present on the oxide surface. OH groups functioning asreactive sites a so-called ligand exchange reaction takes place in whicha covalent bond is formed between the surface and the source material(chemisorption). When the oxygen bridges are concerned a dissociatingreaction takes place in which reaction a covalent bond is also formed(chemisorption). The bond formed by chemisorption is very strong and thesurface structure formed on the surface is stable which enables thesaturation of the surface by one molecular layer. The ligand exchangereactions are carried out by leading the gaseous or vaporized sourcematerials alternately into the reactor and by purging the reactor withan inert gas between the pulses of the source materials (T. Suntola,Thin Solid Films 215 (1992) 84; Niinistö et al. Materials Science andEngineering B 41 (1996) 23). Also even and uniform films can be grown byALCVD even on large surface areas. Accordingly films can be grown onboth even and heterogeneous surface as well as on a grooved surface.Controlling the thickness and the composition of the film by means ofthe number of reaction cycles is precise and simple.

Silicon dioxide has also been grown by the ALD process. CompoundsSi(NCO)₄ and N(C₂H₅)₃ (K. Yamaguchi et al., Appl. Surf. Sci. (1998)130-132) have been used as source materials. Producing silicon dioxideby Molecular Layer ALE and UHV-ALE processes using SiCl₄ and H₂O assource materials is also known in the literature (Surface Review andLetters, Vol. 6, Nos 3 & 4 (1999) 435-448).

The disadvantages of these known solutions are long reaction times, forwhat reason the proposed processes cannot be realized on an industrialscale.

The objective of the present invention is to eliminate the disadvantagesrelated to the prior art and to provide a novel method, which enables acontrolled growth of SiO₂ containing thin films with sufficiently shortreaction times.

The invention is based to the discovery that the above mentionedobjectives can be achieved by using a silicon compound containing anorganic ligand as the silicon source and a reactive oxygen source, suchas ozone, as the oxygen source material. Multicomponent oxides in whichthe amount of silicon dioxide can be varied in a controlled way caneasily be prepared by the proposed solution.

Furthermore, in the connection of the invention it has surprisingly beenfound that while growing multicomponent oxides, i.e. “tertiary oxides”,by the ALD method from the corresponding source materials of silicon andsome other semimetal or metal and by using suitable oxygen sources thegrowth rate of the multicomponent oxide is higher than that of eitherindividual oxide. According to the invention the multicomponent oxidesare therefore prepared by binding from the gas phase a suitable,vaporised silicon compound onto the growth substrate, converting thebonded silicon compound to silicon dioxide, bonding from the gas phase avaporised metal compound or a vaporised compound of another semimetalonto the growth substrate and converting the bonded metal compound orthe compound of another semimetal to a corresponding oxide whereby thesilicon compound and the compound of another semimetal and/or metal arebonded onto the growth substrate in a desired order.

More precisely, the method for preparing oxide films according to thefirst embodiment of the invention is characterized by what is stated inthe characterizing part of claim 1.

The method of preparing multicomponent oxide films according to theinvention is in turn characterized by what is stated in thecharacterizing part of claim 20.

Remarkable advantages are achieved with the aid of the invention. Thus,the ALD process provides a possibility for growing a multistagedinterlayer containing both silicon dioxide and metal oxide prior togrowing the actual metal oxide, which has a high dielectricity. Thestability of the capacitor dielectric can be increased by mixingamorphous silicon dioxide into the dielectric. The preparing ofmulticomponent oxides and the advantages achieved thereof are describedin more detail below.

It is to be noted that with the aid of the invention also pure silicondioxide films can however be prepared. Such a silicon dioxide materialcan be used further in so-called STI (shallow trench isolation)structure. The function of STI is to isolate the transistors from eachother in both the circuit and memory structures. At present in thelateral direction wide so-called LOCOS isolation is in use, whichisolation is not suitable in the future circuits because of itsbulkiness. In STI technology a horizontal narrow deep trench filled withdielectric=silicon dioxide, is etched between the circuits. Since thedepth of the trench is greater than the width STI requires a methodwhich is capable of filling the etched isolation trench conformally. Bythe conventional CVD method STI trenches can be filled but often thetrench has to be widened in the upper part in order to avoid voidformation in the middle of the STI isolation. Enlargement of the trenchleads to increase of the STI area, i.e. the area of the isolation areaincreases. ALD is an especially suitable process for producing STIbecause ALD is characterized by the ability to grow silicon dioxide ofuniform quality and without void formation on uneven growth substrates,especially also onto narrow trenches. Using ALD enables thus a narrowerisolation area between the circuits whereby the packing density of thecircuits can be increased.

In the components needed in magnetic recording silicon dioxide can beused as the isolation layer in both the writing/reading head and in theencapsulation of the writing/reading head. In order to avoid thedestruction of the magnetic properties of the layers, that are alreadybuilt, the processing temperature must be low in all steps. In general,physical (sputtering) methods are used in the field, the problem of saidmethods being the unevenness of produced film. ALD has the capability toproduce both physically and electrically homogenous thin film. It isespecially preferable to use a low temperature ALD silicon dioxideprocess that provides a uniformly covering and electrically homogenousSiO₂ thin film. In this way the reproducibility and reliability of thisprocess step can be increased.

In the field emission displays (FED) film deposition methods producinguniform thin film on a large surface are needed. Due to the low growthtemperature and the uniformity of the silicon dioxide film produced theALD silicon dioxide process is very suitable for preparing thedielectric layer for the field emission displays.

By using especially reactive oxygen sources such as ozone, peroxide andoxygen radicals for converting the bonded silicon compound the formingtemperature of silicon dioxide can be significantly decreased. Accordingto the invention it can be operated especially at a temperature lowerthan 450° C., most preferably at 400° C. at the most. In that case thewhole growing cycle can also be accomplished at the same temperature,which has a great significance for industrial processing. Additionally,by using these reactive oxygen sources a very wide group of organicsilicon compounds, which are not possible to be converted by e.g. water,become available.

In the following the invention is viewed more closely with the aid of adetailed description.

In the solution according to the invention silicon dioxide thin filmsand films mixed with silicon dioxide are grown in the ALD reactorpreferably at the temperature of 150-450° C. Even flat (such as glass orwafer) or grooved flat materials can be used as a substrate. On thesurface of the substrate can also exist a so-called HSG (hemisphericalgrain) structure on which the film is grown. Additionally, a powderymaterial, which has a large surface area, can be used as a substrate.The term “growth substrate” designates in this invention the surface onwhich the thin film is grown. The surface can consist of the abovementioned substrate or of a thin film grown onto the substrate or ofanother structure.

According to the ALD process the silicon source material is vaporisedand led onto the substrate on which it reacts and forms via a ligandexchange reaction or dissociation reaction one chemisorbed molecularlayer on the surface. After the reaction the reaction space is purgedcarefully with an inert gas to remove the unreacted source material andreaction products from the reaction space. In the connection of thisinvention vaporisable compounds of silicon, which contain at least oneorganic ligand, are used as the silicon source material. “Organicligand” designates a hydrogen carbyl group, which is derived from anorganic compound. Such a ligand has thus itself a C—C bond (e.g. anethyl group) or it is bonded via carbon to the silicon atom or it has aC—H bond(s). According to a preferred embodiment silane, siloxane orsilazane are used as vaporisable silicon compounds. These arecommercially available compounds.

Especially preferably a silicon compound, which has a boiling point of400° C. at the most at a pressure of 10 mbar is selected. Thus the ALDprocess can be carried out in the above mentioned preferred temperaturerange of 150-400° C.

The following can be mentioned as examples of the preferred silane,siloxane and silazane compounds:

Silanes of the FormulaSi_(m)L_(2m+2)  (I)wherein m is an integer 1-3,Siloxanes of the FormulaSi_(y)O_(y−1)L_(2y+2)  (II)wherein y is an integer 2-4, andSilazanes of the FormulaSi_(y)NH_(y−1)L_(2y+2)  (III)wherein y is an integer 2-4.

In formulae (I)-(III) each L can independently be F, Cl, Br, I, alkyl,aryl, alkoxy, vinyl (—CH═CH₂), cyano (—CN), amino, silyl (H₃Si—),alkylsilyl, alkoxysilyl, silylene or alkylsiloxane whereby alkyl andalkoxy groups can be linear or branched and contain at least onesubstituent. Typically alkyl and alkoxy groups contain 1-10 carbonatoms, most preferably 1-6 carbon atoms.

As examples of especially preferred silicon compounds amino-substitutedsilanes and silazanes, such as 3-aminoalkyltrialkoxy silanes, forexample 3-aminopropyltriethoxy silane NH₂—CH₂CH₂CH₂—Si(O—CH₂CH₃)₃(AMTES) and 3-aminopropyltrimethoxy silane (NH₂—CH₂CH₂CH₂—Si(O—CH₃)₃(AMTMS) and hexa-alkyldisilazane (CH₃)₃Si—NH—Si(CH₃)₃ (HMDS) can bementioned.

The silicon compound can also be formed during the ALD process in theconnection of gas-phase reactions so that while the silicon compound isbonding, a new gas-phase silicon compound is formed which in turn isable to bond to the hydroxyl and, optionally oxide groups of the growthsubstrate. In this invention this phenomenon is called “in situ”formation of silicon compound. Such an in situ formed silicon compoundcomprises typically a silane compound, e.g. a silane compound which hasa formula SiL₁L₂L₃L₄, wherein L₁ represents an amino group and L₂-L₄represent alkyl or alkoxy group. This silane compound is formed e.g.when the growth substrate is contacted with hexa-alkyldisilazane at350-450° C. at the pressure of 0, 1-50 mbar.

After bonding the silicon compound a suitable reactive oxygen source isintroduced into the reaction space, said oxygen source providing theconversion of the silicon compound to silicon dioxide on the growthsurface. In the following the invention is described more closely havingozone as an example. It must however be noted that instead of ozone alsoother oxygen source materials, listed below more precisely, can be usedin many cases. Using ozone numerous advantages are however to beachieved as far as the spectrum of the silicon compounds used and theprocessing temperature are concerned.

Ozone, which is introduced into the reaction space, reacts with theligands of the chemisorbed silicon source material forming OH groups andoxygen bridges on the surface. In other words ozone combusts the organicligands and water formed in the combustion reaction forms further OHgroups. After the reaction the reaction space is purged very carefullyagain with an inert gas to remove the unreacted ozone and the reactionproducts. These four steps together form one growth cycle. The growthcycle is repeated until the film has the desired thickness.

A multicomponent film is achieved by changing the source material, i.e.by growing some other oxide onto the growth substrate between silicondioxide growth cycles. From the point of view of the invention thegrowth order of the oxide compounds can be optional.

A multicomponent oxide, usually MSiO_(x), is grown by vaporising themetal source material and leading the vaporised metal source materialonto the substrate on which it reacts forming one molecular layer on thesurface via a ligand exchange reaction and/or dissociation reaction.After the reaction the reaction space is purged carefully with an inertgas to remove the unreacted source material and the reaction productsfrom the reaction space. After this the oxygen source material is ledinto the reaction space, said oxygen source material reacting with theremaining ligands (e.g. chloride ligands) of the chemisorbed metalcompound complex (e.g. zirkonium complex) forming new OH groups andoxygen bridges on the surface. After the reaction the reaction space ispurged again carefully. In the next step the above-described growingcycle of silicon dioxide can be carried out.

In the case of a multicomponent oxide any of the above mentioned siliconsource materials can be used as the silicon compound. It must, however,be noted that also the halide compounds of silicon (silicontetrachloride, silicon tetrafluoride, silicon tetraiodide etc.) as wellas the above mentioned amino compounds are, however, suitable for beingused as silicon source materials. Any of the below specified oxygensources can be used as the oxygen source, most preferably, however,water or ozone.

One or more metals or semimetals can function as the second cation ofthe multicomponent oxide (i.e. tertiary oxide). Metals belonging to thegroups IIIa, IVa and Va (transition metals) of the periodic table of theelements including the rare earth metals, i.e. lanthane and lanthanoids,as well as the metals and semimetals of group IVb can especially bementioned of the metals.

As the source material for the metal or semimetal (e.g. germanium) anystable vaporisable compound of metal in question can be used. In theexample case (see example 2) the following metal source materials wereused: aluminium chloride as aluminium source material, titaniumtetrachloride (TiCl₄) as titanium source material, tantalumpentachloride (TaCl₅) as tantalum source material, hafnium tetrachloride(HfCl₄) as hafnium source material, zirkonium tetrachloride (ZrCl₄) aszirkonium source material, yttrium betadiketonate (Y(thd)₃) as yttriumsource material and lanthanum betadiketonate (La(thd)₃) as lanthanumsource material. In the example cases water steam (H₂O) was used as theoxygen source with aluminium, titanium, zirkonium and hafnium andtantalum source material and ozone (O₃) was used as the oxygen sourcewith lanthanum and yttrium source material.

Multicomponent films containing various concentrations of silicondioxide, e.g. SiAlO_(x), SiTiO_(x), SiTaO_(x), SiHfO_(x), SiZrO_(x),SiYO_(x), SiLaO_(x), can be grown according to the invention by changingthe number of reaction cycles of the silicon source material and ozone.In the formulae above the amount of oxide can vary and the oxide is notalways completely stoichiometric.

The ratio of the amount of the metal oxide and silicon dioxide cyclescan be varied. The number of cycles of the metal oxide can vary between1-1000 and that of silicon dioxide between 1-1000. Preferably the numberof cycles of the metal oxide varies between 1-50 and that of silicondioxide between 1-50. By varying the metal oxide cycle/silicon dioxidecycle ratio in question e.g. between 10:1 . . . 1:10 the nature of themixed oxide can be varied in a controlled way from a complete mixedoxide to a nanolaminate structure.

In growing of multicomponent oxides it has been found that the growthrate of the multicomponent oxide is higher than that of eitherindividual oxide from which the multicomponent oxide is formed. Forexample the growth rate of La₂O₃ from La(thd)₃ and ozone as well as thegrowth rate of Y₂O₃ from Y(thd)₃ and ozone is 0.2 Å/cycle which is atthe same time equal to the growth rate of SiO₂ from 3-aminopropylmethoxysilane and ozone. By preparing the mixed oxide of these metal oxidesmentioned above with silicon dioxide using the cycle ratio of 1:1 agrowth rate of more than threefold, 0.7 Å/cycle, is achieved.

Any oxygen compound suitable for using in the ALD technology canfunction as the oxygen source in the above silicon dioxide andmulticomponent oxide processes. Preferred oxygen source materials arefor example water, oxygen and hydrogen peroxide and the aqueoussolutions of hydrogen peroxide. Most preferably such oxygen sources areused which are more reactive than water towards silicon compound whichcontains an organic ligand. As mentioned above an especially preferredoxygen source material is ozone (O₃). Ozone can be produced by an ozonegenerator and it is most preferably introduced into the reaction spacewith the aid of nitrogen gas (or inert gas of same kind) whereby theconcentration of ozone is about 1-30 vol.-%, preferably about 2-25vol.-%.

By using ozone as the source material organic ligands of silicon sourcematerial, said ligands forming a linear Si—C bond, can be changed atsuch a temperature in which the other possible ligands of the siliconsource material, for example alkoxy ligands, which form a Si—O—C bondare not uncontrolled decomposing.

One or more of the following compounds can also be used as the oxygensource material:

-   -   oxides of nitrogen, such as N₂O, NO and NO₂,    -   oxyhalide compounds, for example chlorodioxide (ClO₂) and        perchloroacid (HClO₄),    -   peracids (—O—O—H), for example perbenzoic acid (C₆H₅COOOH) and        peracetic acid (CH₃COOOH),    -   alcohols, such as methanol (CH₃OH) and ethanol (CH₃CH₂OH), and    -   various radicals, for example oxygen radical (O..) or hydroxyl        radical (.OH).

The following non-limiting examples illustrate the invention:

EXAMPLE 1

SiO₂ films were grown in a flow type F-120 ALCVD™ reactor (ASMMicrochemistry Ltd.). 3-aminopropyltriethoxy silaneNH₂—CH₂CH₂CH₂—Si(O—CH₂CH₃)₃ (AMTES), 3-aminopropyltrimethoxy silane(NH₂—CH₂CH₂CH₂—Si(O—CH₃)₃ (AMTMS) and hexamethyldisilazane(CH₃)₃Si—NH—Si(CH₃)₃ (HMDS) were used as the silicon source material.Ozone (O₃) was used as the oxygen source material. AMTES and AMTMS wereinside of the reactor. Ozone and HMDS were led into the reactor fromoutside. The reaction temperature of AMTES was 200 or 300° C., that ofAMTMS 300° C. and HMDS 400° C.

The growing of SiO₂ from AMTES was carried out with the aid ofalternating AMTES and ozone pulses between of which the reaction spacewas purged carefully so that the source materials would not besimultaneously present in the reaction space. The duration of the AMTESpulse was 1.0 s and that of the purging pulse 2 s. The duration of theozone pulse was 4.0 s and the duration of the purging pulse 4.0 s. Thegrowth rate of SiO₂ was 0.15 Å/reaction cycle at the reactiontemperature of 300° C. and 0.28 Å/cycle at the reaction temperature of200° C. The refractive index of silicon dioxide grown at 300° C. was1.4. Using AMTMS as the source material the pulsing times were 0.5 s,0.5 s, 2.0 s and 1.0 s, respectively, and the growth rate was 0.16Å/reaction cycle.

The growing of SiO₂ from HMDS was carried out in the same way as above.The duration of the HMDS pulse was 0.5 s and that of the purging pulse 2s. The duration of the ozone pulse was 2.5 s and that of the purgingpulse 1 s. The growth rate was 0.17 Å and the value of the refractiveindex varied between 1.48-1.57.

Based on the results, ozone can be used together with the vaporisablesilicon source material for growing silicon dioxide by the ALD process.Of the silicon source materials the advantage of AMTES and AMTMS is thelow reaction temperature when ozone is used as the oxygen source. Thisenables further the preparing of multicomponent oxides since other thanmetal chlorides do not stand reaction temperatures above 350° C. withoutdecomposing.

EXAMPLE 2

Multicomponent oxides were grown in the above reactor using AMTMS as thesilicon source material. In the growing processes the AMTMS pulse was0.5 s, the purging pulse 0.5 s, the ozone pulse 3.5 s and the purgingpulse 1 s. The pulse of the metal source material was correspondingly0.5 s and the purging pulse 0.5 s. If water was used as the oxygensource the duration of the water pulse was 0.2 s and that of the purgingpulse 0.5 s. Using ozone with the metal source material the duration ofthe ozone pulse was 3.5 s and that of the purging pulse 0.5 s. Thegrowth rates and cycle ratios are shown in the table below.

Total amount of Multicomponent Metal source cycles/Cycle ratio oxidematerial (M:S) Growth rate Å/cycle SiTiOx TiCl₄ 1800/(1:1) 0.9 SiTaOxTaCl₅ 1800/(1:1) 1.1 SiHfOx HfCl₄  700/(1:1) 1.23 SiZrOx ZrCl₄ 700/(1:1) 1.1 SiZrOx (repeat) ZrCl₄  700/(1:1) 1.1 SiAlOx Al(CH)₃1900/(1:1) 1.0 SiLaOx La(thd)₃ 1100/(1:1) 0.75 SiYOx Y(thd)₃ 1100/(1:1)0.73 SiYOx Y(thd)₃ 2200/(2:2) 0.74 SiYOx Y(thd)₃ 2200/(5:5) 0.72 SiYOxY(thd)₃  2200/(10:10) 0.70 SiYOx Y(thd)₃  2200/(20:20) 0.64 SiYOxY(thd)₃  2240/(40:40) 0.20 M = number of the cycles of the metal sourcematerial, S = number of the cycles of the silicon source material

The multicomponent samples were analyzed by ESCA (electron spectroscopyfor chemical analysis). The thin film samples were analyzed in threedifferent sites showing that the multicomponent oxides were veryhomogenous. Furthermore, the multicomponent oxides were very uniformwhich is typical for the ALD process when the chemistry of the growingis favourable.

1. An atomic layer deposition (ALD) process for producing a thin filmcomprising silicon dioxide on a substrate by alternating, saturatingsurface reactions, the process comprising: contacting a substrate in aflow type reactor with a vaporized silicon compound selected from thegroup consisting of amino substituted silanes and silazanes, wherein asubstrate temperature is selected such that the silicon compoundchemisorbs to the substrate to form a single molecular layer and doesnot condense or decompose on the substrate, said silicon compoundcomprising at least one organic ligand; removing unreacted siliconcompound; and converting the chemisorbed silicon compound into silicondioxide by contacting it with a reactive vaporized oxygen sourcecompound, wherein the reaction temperature is selected such that thesilicon compound does not condense or decompose on the substratesurface; wherein the vaporized silicon compound and the reactivevaporized oxygen source compound are the only reactants used to form thesilicon dioxide; and wherein when each reactant is contacting thesubstrate, the reactant flows continuously from an inlet of the reactorto an outlet of the reactor.
 2. The process of claim 1, wherein theboiling point of the silicon compound is less than or equal to 400° C.at a pressure of 10 mbar.
 3. The process of claim 1, wherein the siliconcompound is selected from the group consisting of silicon compounds ofthe formula:Si_(y)NH_(y−1)L_(2y+2),  (I) wherein y is an integer from 2 to 4 andeach L can independently be F, Cl, Br, I, alkyl, aryl, alkoxy, vinyl(—CH═CH₂), cyano (—CN), amino, silyl (H₃Si—), alkylsilyl, alkoxysilyl,silylene or alkylsiloxane, wherein the alkyl and alkoxy groups can belinear or branched and contain at least one substituent, with theproviso that at least one L is an organic ligand.
 4. The process ofclaim 1, wherein the silicon compound comprises both an alkyl and analkoxy group, at least one of which may be substituted.
 5. The processof claim 4, wherein the silicon compound is selected from the groupconsisting of 3-aminoalkyltrialkoxy silane and hexa-alkyldisilazane,wherein the alkyl and alkoxy groups comprise from 1 to 10 carbon atoms.6. The process of claim 1, wherein the substrate comprises hydroxylgroups on the surface thereof that are reactive with the siliconcompound.
 7. The process of claim 6, wherein a second silicon compoundthat is capable of reacting with the hydroxyl groups is formed in situ.8. The process of claim 7, wherein the second silicon compound is asilane.
 9. The process of claim 8, wherein the formula of the silane isSiL₁L₂L₃L₄, wherein L₁ represents an amino group and L₂-L₄ representalkyl or alkoxy groups.
 10. The process of claim 7, wherein the secondsilicon compound is formed by contacting the substrate withhexa-alkyldisilazane at 350-450° C. at a pressure of 0.1-50 mbar. 11.The process of claim 1, wherein the substrate comprises oxide groups onthe surface thereof that are reactive with the silicon compound.
 12. Theprocess of claim 1, wherein the reactive oxygen source compound isselected from the group consisting of water, oxygen, hydrogen peroxide,an aqueous solution of hydrogen peroxide, ozone and a mixture thereof.13. The process of claim 1, wherein the reactive oxygen source compoundis a nitrogen oxide.
 14. The process of claim 13, wherein the reactiveoxygen source compound is selected from the group consisting of N₂O, NOand NO₂.
 15. The process of claim 1, wherein the reactive oxygen sourcecompound is selected from the group consisting of oxyhalides, peracids(—O—O—H), alcohols, oxygen radicals (O..) and hydroxyl radicals (.OH).16. The process of claim 15, wherein the oxyhalide is selected from thegroup consisting of chlorine dioxide (ClO₂) and perchloro acid (HClO₄).17. The process of claim 15, wherein the peracid is selected from thegroup consisting of perbenzoic acid (C₆H₅COOOH) and peracetic acid(CH₃COOOH).
 18. The process of claim 15, wherein the alcohol is selectedfrom the group consisting of methanol (CH₃OH) and ethanol (CH₃CH₂OH).19. The process of claim 1, wherein the bonded silicon compound isconverted into silicon dioxide by contacting it with ozone-containinggas having a ozone concentration of 1-30 vol.-%.
 20. The process ofclaim 1, wherein contacting the substrate with a vaporized siliconcompound and converting the bonded silicon compound into silicon dioxideare both performed at essentially the same temperature.
 21. The processof claim 1, wherein the thin film consists essentially of silicondioxide.
 22. The process of claim 1, wherein the thin film is amulticomponent oxide thin film comprising silicon dioxide and one ormore additional oxides.
 23. The process of claim 22, wherein theadditional oxide is selected from the group consisting of zirconiumoxide, titanium oxide, hafnium oxide, tantalum oxide, aluminum oxide,yttrium oxide and lanthanum oxide.
 24. The process of claim 23, whereinthe additional oxide is produced by contacting the substrate with ahalide compound selected from the group consisting of vaporized halidecompounds of zirconium, aluminum, titanium, hafnium, and tantalum, suchthat the halide compound bonds to the substrate and converting thebonded halide compound into an oxide by contacting it with a vaporizedreactive oxygen source compound.
 25. The process of claim 24, whereinthe reactive oxygen source compound comprises water.
 26. The method ofclaim 1, wherein the reactive vaporized oxygen source compound is notwater.
 27. An atomic layer deposition (ALD) process for producing a thinfilm comprising silicon dioxide on a substrate by alternating,saturating surface reactions, the process comprising: contacting asubstrate in a flow type reactor with a vaporized silicon compoundselected from the group consisting of amino substituted silanes andsilazanes, said silicon compound comprising at least one organic ligand;removing unreacted silicon compound; and contacting the substrate withan ozone-containing gas; wherein the vaporized silicon compound and theozone-containing gas are the only reactants used to form the silicondioxide; and wherein when each reactant is contacting the substrate, thereactant flows continuously from an inlet of the reactor to an outlet ofthe reactor.
 28. The process of claim 27, wherein the ozone-containinggas has a ozone concentration of 1-30 vol.-%.
 29. The process of claim27, wherein the ozone-containing gas has a ozone concentration of 2-25vol.-%.